SU124570A1 - The method of obtaining polymethine dyes, optical sensitizers halide-silver emulsions where B - non-metallic atoms needed to build residues of ketomethylene cyclic compounds, for example - Google Patents

Description

where B is the non-metal atoms necessary to build residues of ketomethylene cyclic compounds, for example, 3-alkyl (klp aryl) -rodanines, 3-alkylorodanines, 3-alkyloxazolidin-2-ones 4, 1-phenyl-3-methyl-nerazolone and others; R is an alkyl, aryl or substituted alkyl group, one mole of a quaternary 5-anilinomethylenerodanine salt of the formula

. j

;

I I (M

,,.,

where R - has the indicated meaning: R — CH 2 or CaHs, and X is an acid residue, is condensed with two moles of a cyclic ketomethylene compound of the general formula:

But ..

where B has the above value in a mixture of niridine, acetic anhydride and triethylamine either by heating or at room temperature, but dyes are isolated in the usual way.

It has been found that oxaneomericiai of the general formula I sensitize the halogen-silver photographic emulsion to different parts of the spectrum, depending on the nature of the extreme heterocyclic residues (substituent B in the formula of general structure I).

The photographic efficacy of these dyes does not change in the presence of the non-diffusive color-forming components of a series of 1,2-hydroxy naphthoic acid amides.

For oxanomericanines containing as extreme heger-residues (substituent B in formula I) residues of 3-substituted rodania, the presence of a sensitivity failure in the blue-green region (500-560 mmk) is characteristic.

Oxanomeriocyanines are introduced into a photographic emulsion before watering in the form of a methanol or ethanol solution.

The optimal concentrations, depending on the nature of the extreme heterocyclic residues (substituent B in formula I), range from 32 to 10 moles of dye per 1 mole of silver in the emulsion.

Example 1. A mixture of 0.53 g of 3-ethyl-5-anilno.1. Tetyleyrodanine and 0.38 g of dimethyl sulfate is heated for 10 minutes. at 115-120. To the still hot ethylmethylsulfate 2-methylmercapto-3-ethyl-5-anilinomethylenethiazolinone-4 (II,,, X CH3504) was added 0.64 g of 3-ethylrodanine, 2.2 ml of acetic anhydride, 7 ml of iiridine, 1, 4 ml of triethylamine and the reaction mixture is stirred for 2 hours. at normal temperature, and then left overnight.

The next day, the precipitated precipitate is filtered, washed with water, alcohol, benzene and ether.

The weight of 3-ethyl-2- 3-ethylthiazolpredine-2-one-4-ylnden-5 -5-3-ethyl-4 oxythiazolin-2-yl-5-methylene thiazolinone 4--0.56 g. So pl. 219-

220 (with decomposition). (Deputy B in formula I-carbon 3-ethylrodiene).

The dye is boiled with e benzene (2 times 50 ml) and crystallization from ethanol (1: 500). The output of 0.28 g (30.4%). Green crystals with m. PL. 236-238 (with decomposition). Maximum alcohol content in ethyl alcohol at 594 .ir.-j / c.

75 ml of a 0.14So methyolyugo solution of this dye is injected into a 1 / g solution of bromide discharging by emulsion. After 20 minutes, 1: stand in a thermostat at 40 ° oi; o poured on ilastiki or ilenku. A highly sensitive photographic material is obtained that is sensible to the zone of 560-700 liters: a micron with a maximum at 650 mmk and a pronounced sensitivity dip in the region of 500-560 mmk.

When replacing 3-ethylrodanium with 3phenylrodanine in the corresponding stage of synthesis, 3-ethyl-2-3-phenylthiazolidi-thio-n-2-one-4-ylidene-5-5-3-phenyl-4-oxythiazolithio-2-yl-5 is obtained -metnlen tpazolion-4 (substituent B in formula I is the residue of 3-feiylrodaiine). Output 27.8Vn.

Get small green crystals with t. Il. 190 (with decomposition). The maximum absorption in etiotic ennrte iri 601 MMK. Sensitization area 560-680 MMK. The maximum sensitization is 640 M.V.K. The failure of sensitivity in the region of 500-5bO MMK.

Similarly, a substitution at the appropriate stage of the synthesis of 3-eti.prodanin on 1-feiyl-3-methylpyrazoloi is obtained with a yield of 32.6% 3-ethyl-2 (H-phenyl-3-methyl-pyrazolidi-ylidene-4) -5- (1-phenyl-3 -methyl5 -oxypyrazole-4-methyles) thiazolinone-4.

Receive orange prisms with t. Pl. 275 ° (with decomposition). (Deputy B in formicle I-residue 1-phenyl-3-methylpyrazole). Maximum absorption in ethyl alcohol at 520 kms. The maximum sensitization at 605 MMK; failure in sensitivity in the region of 510-550 .. t. / s.

Example 2. A mixture of 0.53 g of 3-ethyl-5-anilino-methyryodainine to 0.38 g of dimethyl sulfate is heated for 10 minutes. at 120. 0.88 g of 3-carbethoxymethylrodanine, 2.2. ethyl acetic anhydride, 7 ml of pyridine, 1.4 /; U-triethyl 1 inna and 1 ml of polymethyl sulfate 2-methyl mercate-3-methyl-5-anilinomethylene thiazolinone-4; the reaction mixture is stirred for 1 hour at normal temperature.

The next day, the dye does not fall out and therefore the mixture is evaporated in vacuo, the residue is washed with 160 ml of hot benzene (4 times 40 ml), after which it is dissolved in 40 g of chloroform and the solution is chromatographed on alumina. Oxanomerimane} P1 is desorbed from alumina with a mixture of chloroform and alcohol (1: 1). The resulting filtrate is evaporated to dryness in vacuo, and the residue is crystallized twice from ethyl alcohol (1: 30). The output of the 3-ethnl-2 (3-carbethoxy-methyltnazolidin-2-one-4-nlidene-5) -5- (3 - carbethoxymethyl-4 - oxythiazolin-2-yl-5-methyly) thiazolinium-4-0.40 g (35.1; o). Dark blue crystals are obtained with m. Il. 199-200 (as laid down i). Maximum absorption in ethyl alcohol at 591 μm.

75 ml of a 0.017% methanol solution of this dye is injected into 1.g of molten alumina negative bromodo-silver emulsion. The resulting photographic material is sensible to the 560-700 mmk zone with a maximum of 640 mmc and a sensitivity dip in the range of 500–560 m .. mc.

With a substitution on the corresponding stadn synthesis of 3-carbethoxymethylrodanine 3-carboxymethylrodanine and the subsequent treatment of the reaction solution with ether, hot benzene and chloroform, a yield of 38.4% of 3-ethyl-2 (3-carboxymethylthiazolidine-2-he-4-or-3) is obtained -L

M 124570

den-5) -5- (3 -carbo1 simethyl-4-oxythiazolin-thiop-2-yl-5-methyl 11) thiazolino-4. Dark blue plates are obtained with a pl. 189-190 ° (with decomposition). Maximum absorption in ethyl alcohol at 597 MMK. Maximum sepsibilization at 645 MMK.

Example 3. A mixture of 0.53 g of 3-ethyl-5-anilinomethylenerodanine and 0.46 g of diethyl sulfate is heated for 20 minutes. at 120-125 °, then 0.64 g of 3-ethylisorodanine, 2.2 ml of acetic anhydride, 7 ml of pyridine, 1.4 ml of triethylamine are added, the reaction mixture is stirred for 1 hour and left overnight.

To isolate the dye, the reaction mixture is evaporated in vacuo, the residue is dissolved in chloroform and the solution is chromatographed on oxy-aluminum. Oxanomeriocanine is desorbed with alumina and a mixture of chloroform and alcohol (3: 2) is washed into the filtrate.

The filtrate is evaporated in vacuo and the residue is boiled twice with a mixture of benzene and alcohol (9: 1).

Yield 0.1 g (11%). Receive dark-violet prisms with t. Nl. 171-172 ° (with decomposition). Maximum absorption in ethyl alcohol at 624 kms. Maximum sensitization at 660 MJHK.

Subject invention

A method for producing polymethine dyes, optical sensitizers for halo-silver emulsions, characterized in that, in order to obtain OX-3-mocyanine in the general formula.

where B is non-metal atoms required to build residues of ketomethylene cyclic compounds, for example, 3-alkyl (or aryl) -rodanines, 3-alkyl-isorodanines, 3-alkyloxazolidin-2-ones 4, 1-phenyl-3-methylpyrazolone and others, R - alkyl, aryl or substituted alkyl group, one mole of quaternary salt of 5-anilinomethylenerodanines of the formula

Syn S

, (N) -sr